Hydrolysis of Dimethyl Methylphosphonate (DMMP) in Hot-Compressed Water

J Phys Chem A. 2020 Oct 15;124(41):8383-8389. doi: 10.1021/acs.jpca.0c05104. Epub 2020 Sep 30.

Abstract

Dimethyl methylphosphonate (DMMP) is often used as a chemical surrogate for organophosphate nerve agents, as it exhibits similar physiochemical properties while having significantly lower toxicity. Continuous hydrolysis of DMMP in hot-compressed water is performed at temperatures from 200 to 300 °C, pressures of 20 and 30 MPa, and residence times from 30 to 80 s to evaluate the effects of pressure and temperature on reaction kinetics. DMMP hydrolysis is observed to follow pseudo-first-order reaction behavior, producing methylphosphonic acid and methanol as the only detectable reaction products. This is significant for the practical implementation of a continuous hydrothermal reactor for chemical warfare agent neutralization, as the process only yields stable, less-toxic compounds. Pressure has no discernible effect on the hydrolysis rate in compressed liquid water. Pseudo-first-order Arrhenius parameters are determined, with an activation energy of 90.17 ± 5.68 kJ/mol and a pre-exponential factor of 107.51±0.58 s-1.